CN117512629A - Natural gas vapor self-heating conversion and water electrolysis mixed power hydrogen production and fuel cell coupled cogeneration system - Google Patents
Natural gas vapor self-heating conversion and water electrolysis mixed power hydrogen production and fuel cell coupled cogeneration system Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/60—Constructional parts of cells
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C25B15/00—Operating or servicing cells
- C25B15/02—Process control or regulation
- C25B15/021—Process control or regulation of heating or cooling
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
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- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/60—Constructional parts of cells
- C25B9/67—Heating or cooling means
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Abstract
The invention discloses a natural gas steam self-heating conversion and water electrolysis hybrid hydrogen production and fuel cell coupled heat and power Cogeneration (CHP) system, which consists of a Hybrid Hydrogen Production (HHP) subsystem and a proton membrane fuel cell (PEMFC), wherein the HHP subsystem consists of an energy source raw material module, a self-heating conversion (ATR) hydrogen production module, a proton exchange membrane water electrolysis (PEM) hydrogen production module and a Pressure Swing Adsorption (PSA) hydrogen extraction module, and the PEMFC subsystem consists of a PEMFC module, an alternating current-direct current conversion (DC/AC) module and a Waste Heat Recovery (WHR) module.
Description
Technical Field
The invention belongs to the technical field of preparation and cogeneration application in hydrogen energy sources, and particularly relates to a cogeneration system with natural gas and water vapor self-heating conversion and water electrolysis mixed motion hydrogen production and fuel cell coupling.
Background
Hydrogen energy is one of the most promising clean secondary energy sources at present, is an important tie of traditional natural gas and other energy forms, and has remarkable significance for realizing the coupling of electric power, heat energy, cold energy, renewable energy sources and the like with natural gas. Hydrogen fuel cells are one of the most important technical carriers for hydrogen energy, wherein in the application of combining hydrogen energy with fuel cells and urban fuel gas or urban and rural biomass biogas, the fuel gas or biogas is mainly converted into high-purity H by water vapor 2 The proton exchange membrane hydrogen fuel cell (PEMFC) is a typical fuel which is mainly applied to two fields of automobile and cogeneration at present, has the advantages of low working temperature, good starting performance, high power density and the like, and is very suitable for being applied to occasions of distributed power generation and small and medium-sized application, wherein the power level of the PEMFC reaches megawatt. As the power level increases, its application area will be more extensive. For example, 250kW natural gas reforming hydrogen production-fuel cell power station developed by BALLARD company of Canada has a power generation efficiency of 31% and is used as standby power for post offices and hospitals; U.S. Plug Power, idatech, germany 5kW home power systems were developed for siemens and the like. The japan is mainly focused on the cogeneration field, the application of the PEMFC battery is greatly superior to that of an automobile, hundreds of companies are developing and commercialized gradually, the total loading of the PEMFC cogeneration power station is more than 210kW (2010), and the selling price of the 1 kW-class household cogeneration is less than 35 ten thousand yen: rated direct current (AC) power generation efficiency is 33%, rated thermal efficiency is 40%, and lifetime is 1 ten thousand hours or more than 3 years. However, the heat and power (CHP) energy system formed by coupling the natural gas vapor conversion hydrogen production and the proton membrane fuel cell still has the following problems:
first, although natural gas steam is converted to hydrogen to produce H 2 The cost is the lowest compared with all other hydrogen production methods, but the preparation process has more CO emission 2 Or H obtained from CO or other contaminants 2 The product gas is named as 'gray hydrogen' rather than environmental protection, even if CO is carried out 2 Capturing or utilizing, H 2 The product is called blue hydrogen, the cost is increased, and particularly, the cost of gray hydrogen or blue hydrogen is greatly increased for small-scale or distributed hydrogen production combined with CHP.
Second, the hydrogen production method by natural gas steam reforming mainly comprises steam reforming (SMR), partial Oxidation Reforming (POR), oxygen-enriched combustion reforming (OECR), autothermal reforming (ATR), and plasma reforming, wherein SMR is the most mature and common traditional hydrogen production method, and its core technology is a reformer or a reforming reactor, usually a radiant chamber (section) provides heat to enable the reforming temperature required by the catalytic reforming reaction of methane and steam in a tube in the furnace to be up to 700-850 ℃, and because the volume of the tube-in-tube reformer is limited by radiation heat transfer mode, the miniaturization difficulty of the device is increased, and a certain amount of natural gas is consumed as fuel gas to generate a great amount of surplus steam, thereby increasing the consumption of natural gas and the emission of flue gas, and reducing H at the same time 2 The output rate, which leads to low efficiency of the distributed CHP cogeneration system, is generally 0.25 to 0.40Nm of natural gas which is consumed for 1kW of power supply 3 And due to the addition of the natural gas reforming process, the whole system volume is increasedThe structure is complex and is not suitable for a mobile device. In the aspect of mobile power devices and mobile power sources, a natural gas reforming hydrogen production system is generally separated from a fuel cell system, and hydrogen produced by reforming natural gas is collected and then supplied to the fuel cell as fuel.
Third, proton membrane fuel cells (PEMFCs) themselves generate waste heat to supply heat and often still have residual heat to waste. The heat efficiency, the electric efficiency and the total efficiency of the CHP cogeneration system are almost linearly increased along with the increase of the heat flow of the natural gas and the utilization rate of the hydrogen, so that the higher the natural gas hydrogen production efficiency is, the better the natural gas hydrogen production efficiency is under the condition of a certain occupied area and the same output thermoelectric power, and the higher the traditional natural gas water vapor SMR conversion efficiency is, the more difficult the skid-mounted or mobile miniaturization is. In addition, the fluctuation of the natural gas market or the instability of the pipe network gas leads to the instability of hydrogen production output, and further greatly influences the output thermoelectric load and power of the fuel cell.
Fourth, most of the combustion elements needed by the reforming and conversion of natural gas steam to hydrogen and PEMFC are air-fed through natural gas or H 2 With O in air 2 The combustion reaction takes place to provide heat and operating temperature, but the component with the largest proportion in the air is inert gas N 2 The volume of the combustion chamber is increased greatly, and pollutants such as NOx and the like are easy to generate and are discharged into the atmosphere.
Fifth, for some of the problems associated with conventional natural gas steam reforming SMR processes, autothermal reforming (ATR) is a very potential method of maintaining the heat balance of the reaction system by substantially self-sustaining the energy in the hydrocarbon steam reforming process, and yet producing waste heat in the production process, ATR reforming is a gas-making (hydrogen or syngas) process that combines highly exothermic non-catalytic partial oxidation of methane with highly endothermic steam reforming, which produces the heat required for gasification by combusting the partially converted feedstock in a reactor, thus requiring the addition of oxygen-enriched or pure oxygen. Autothermal reformers (ATRs) are typically pressure vessels with refractory lining, top mixers to ensure gas-water mixtures and The preheated oxygen is quickly and uniformly mixed to perform the catalytic combustion-free reaction, the fluid enters a bed layer with a conversion catalyst loaded at the lower part at the temperature of up to 800-1000 ℃, sufficient heat is provided for the endothermic steam conversion reaction to perform the reaction, and the formed conversion gas is subjected to heat exchange to output high-temperature steam and then is subjected to medium-high temperature conversion reaction and PSA or other purification to obtain high-purity H 2 Product gas. The method has the advantages that external heat supply needed by the traditional natural gas steam SMR reforming conversion hydrogen production is changed into self (internal) heat supply, the utilization of reaction heat is reasonable, the high temperature in a reactor (a reformer) can be limited, the energy consumption, the cost and the use of fuel gas of a conversion system can be reduced, steam is introduced in the process, the carbon deposition and the inactivation of a catalyst are greatly reduced, a huge SMR process radiation section heat transfer system is not needed, carbon particle dust is not needed, the investment and the cost are correspondingly reduced, and the method is suitable for miniaturized skid-mounting of a natural gas steam conversion hydrogen production system, so that the integrated heat and power combined energy system is formed by matching with a PEMFC fuel cell. However, the biggest problem of ATR process is that oxygen-enriched or pure oxygen is required to be introduced, and then additional investment of air separation oxygen-making or PSA oxygen-enriched device is required, so that the cost is greatly increased. Air is introduced to replace oxygen-enriched or pure oxygen, the process is feasible and the cost is low, but O in the air 2 The flow rate and the concentration of the natural gas raw gas, the flow rate of methane content and the like greatly influence the conversion rate of methane and H in the converted gas 2 Concentration of/CO and can introduce difficulties with H in the conversion gas 2 The separated inert gas components such as nitrogen, argon and the like seriously affect the subsequent purification of H 2 And thus has a great influence on the power generation efficiency of the PEMFC fuel cell, and also causes the volume of the combustion chamber to be greatly increased. In addition, the effective gas H in the required conversion gas is obtained by ATR conversion 2 And CO composition, H is required to be introduced 2 Further consume produced H 2 Product gas.
Sixthly, the working principle of proton exchange membrane water electrolysis (PEM) hydrogen production is contrary to that of proton membrane hydrogen fuel cell (PEMFC), and H with higher pressure and purity can be obtained from PEM water electrolysis hydrogen production 2 Through purifying treatmentCan be directly used for PEMFC power generation or cogeneration, but PEM hydrogen production requires power consumption and heat source, and simultaneously, produces by-product O with higher purity 2 The utilization efficiency of the hydrogen production is seriously influenced by the economy and the efficiency of the hydrogen production. Although PEMFC systems can use oxygen-enriched or pure oxygen instead of air, if pure PEM hydrogen production is coupled to the PEMFC power generation process, the energy of the overall system is imbalanced by the net input of additional little energy required for PEM hydrogen production, and such coupling is of no practical significance. Besides, the PEM hydrogen production working medium can adopt a new material membrane with temperature resistance and swelling resistance to handle the electrolytic hydrogen production working condition of water vapor and the operating temperature of 100-120 ℃ besides the conventional hot water and the operating temperature of 60-100 ℃, and has higher hydrogen production efficiency, but needs to consume more heat energy. And the heat generated in the PEMFC power generation is insufficient to be supplied. If the PEM hydrogen production system is heated by adopting electric energy, the response time of the PEM hydrogen production system is slow, the electric energy is further consumed, hydrogen-containing tail gas generated by the PEMFC system cannot be utilized and recovered, and the hydrogen utilization rate is low, so that the efficiency of the PEMFC system is further reduced.
Disclosure of Invention
In order to solve the problems of the existing distributed cogeneration energy (CHP) system with coupling of natural gas and steam reforming hydrogen production and proton exchange membrane water electrolysis (PEM) fuel cells, the primary object of the invention is to provide a compact and efficient cogeneration system with energy transfer, reforming efficiency and energy balance, which can realize the hydrogen production modularization of the natural gas pipe network or the power grid resource supply condition of the distributed cogeneration area by utilizing hydrogen energy nearby, and is effectively coupled with a fuel cell, wherein the hydrogen production raw material structure comprises a distributed home, a hydrogenation station or a building hydrogen supply mode, and the hydrogen production raw material structure comprises a hydrogen production raw material structure, wherein the energy demand and advantages of the natural gas and steam reforming hydrogen production and the water electrolysis PEM are fully utilized, and the hydrogen production raw material structure comprises a distributed home, a hydrogen station or a building hydrogen supply mode, and a hydrogen supply mode, and the hydrogen production and the hydrogen supply mode is further combined with the proton membrane fuel cells after the hydrogen production is formed by efficient coupling of the mixed hydrogen production module with the proton exchange membrane water electrolysis (PEM) hydrogen production module The coupling forms a distributed cogeneration energy system, overcomes the defects that ATR hydrogen production needs oxygen, PEM hydrogen production needs a heat source, PEMFC cogeneration needs stable and sufficient hydrogen supply capacity and the defects existing respectively under the energy balance and material balance of the cogeneration system for realizing hydrogen coupling of hybrid hydrogen production and fuel cells, converts the defects into a combined advantage, reduces the cost of hydrogen energy, and increases the output of green hydrogen and reduces the proportion of gray hydrogen. The technical scheme is that 1, a natural gas steam self-heating conversion and water electrolysis hybrid hydrogen production and fuel cell coupled cogeneration system is provided, which is characterized in that the Cogeneration (CHP) system consists of a Hybrid Hydrogen Production (HHP) subsystem and a proton membrane hydrogen fuel cell (PEMFC) subsystem, wherein the HHP subsystem consists of an energy source raw material module, a proton exchange membrane water electrolysis (PEM) hydrogen production module, a natural gas steam self-heating (ATR) hydrogen production module, a Pressure Swing Adsorption (PSA) hydrogen extraction module, and pipelines, valves and heat exchangers between the modules, the PEMFC subsystem mainly consists of a PEMFC module, a power conversion (DC/AC) module, a Waste Heat Recovery (WHR) module, and pipelines, valves and heat exchangers between the modules, the main flow of the CHP system is that natural gas and desalted water from a city or industrial pipe network are taken as raw materials into the HHP subsystem, the raw material and the raw material and the natural gas and desalted water are all taken into the HHP subsystem, the energy source raw material module and the PEM hydrogen production module are sequentially taken into the HHP subsystem, the hydrogen production module and the hydrogen concentration is 80-99.99% (80-99.99 v/99% hydrogen to 99.99% (99.99/99.99% hydrogen-99% by volume/99% of the water-99.99% by volume/99% of the water/99% by volume conversion/99.v/99% of the water/99.v/99% of the water is produced from the PEM energy water storage system and the energy storage system 2 The product gas enters a PEMFC module of a PEMFC subsystem, direct current output from the PEMFC module outputs alternating current with power of 10 kW-10 MW through a DC/AC module, or is directly used by regional users or is combined with a power grid for use, waste heat generated by the PEMFC module is recycled through a WHR module to output heat of 12 kW-15 MW, a part of the heat is used by regional users for hot water use, a part of the heat is returned to a HHP subsystem for use, the generated cooling water is mixed with the cooling water of the HHP subsystem for recycling after treatment, and the generated H-containing heat is recycled 2 The tail gas is returned to the HHP subsystem as fuel gas, and the concentration generated by the PEM hydrogen production module in the HHP subsystem is 98.5-99.5O of% (v/v) 2 As the fuel gas, a part of the fuel gas is input into an ATR hydrogen production module in the HHP subsystem, a part of the fuel gas is input into a PEMFC module in the PEMFC subsystem, the hydrogenolyzed gas generated by a PSA hydrogen extraction module in the HHP subsystem is taken as the fuel gas, a part of the hydrogen gas is returned to the ATR hydrogen production module in the HHP subsystem, and a part of the hydrogen gas is directly discharged after being treated as the exhaust gas. Wherein, in the HHP subsystem, the energy source raw material module is used for preprocessing natural gas raw materials, treating electric energy, process water, boiler water and steam, optimizing each raw material component and energy to adapt to the requirements of a downstream module, and comprises an ATR hydrogen production module used as raw material natural gas and an PSA hydrogen extraction module used for generating H-containing gas 2 The desorption gas is the supplementary fuel gas, pure oxygen gas, hydrodesulfurization gas, desalted water and steam storage tank, normal temperature or heater or heat exchanger, normal pressure or booster, raw material natural gas desulfurization and treatment of mixed steam of raw material gas and process water, natural gas generator or water and electricity or other power supply, process water and boiler water desalination pretreatment, circulating pump and heat exchange, and process raw materials inside and outside the module, pure oxygen fuel, inlet and outlet pipelines of an electric power pipe network and control valves; the PEM hydrogen production module consists of a one-stage or multistage serial/parallel proton exchange membrane water electrolyzer, a water storage tank/steam tank, a gas-liquid processor, a rectifier, an electric heater, a control system, a throttle valve, a bypass valve and hydrogen (H) 2 ) With oxygen (O) 2 ) Gas cooler, H 2 Catalytic deoxidizer, and power and H connected inside and outside module 2 、O 2 The ATR hydrogen production module comprises a preheating converter of mixed steam, an ATR reformer/reactor with a combustion chamber at the top, a medium-high temperature shift reactor, a gas-liquid separator, a heat exchanger, a steam drum, a waste heat boiler, mixed steam, converted gas, shift gas, fuel gas, PSA stripping hydrogen absorption gas pipeline, desalted water, boiler water supply, a steam storage tank, a cooling circulating water pipeline, a conveying and circulating pump and a control valve, wherein the mixed steam, the converted gas, the shift gas, the fuel gas, the PSA stripping hydrogen absorption gas pipeline, the desalted water are connected inside and outside the module; the PSA hydrogen extracting module consists of a plurality of adsorption towers connected in series/parallel, a desorption gas buffer tank, and electric power and H connected inside and outside the module 2 Product gas/stripping gas, PEMH flowing out of hydrogen production module 2 The device comprises a conversion gas pipeline, a program control valve and a regulating valve group, wherein the conversion gas pipeline flows out of the ATR hydrogen production module.
Furthermore, the cogeneration system for coupling the natural gas steam self-heating conversion with the water electrolysis mixed motion hydrogen production and the fuel cell is characterized in that the purity of the hydrogen production module of the PEM in the HHP subsystem is 99.0-99.99%, and the hydrogen is directly or catalytically deoxidized H 2 H-containing produced with ATR hydrogen production module 2 The ratio of the converted gas with the concentration of 80-90% is 1-4:6-9, and the proportion is prepared by desalted water/process steam, raw material natural gas/fuel gas, process conversion gas and O of a PEM hydrogen production module 2 And/or PSA hydrogen extraction module and/or H-containing of PEMFC module in PEMFC subsystem 2 The control of the usage amount of desorption gas as the supplementary fuel gas flowing out of the waste gas is obtained, wherein the distribution of the flow rates of the process steam entering the ATR hydrogen production module and the preheated desalted water entering the PEM hydrogen production module and the O from the PEM hydrogen production module are controlled by controlling the opening of a water supply pump outlet or/and a bypass steam throttle valve or the opening of a high-temperature steam throttle valve of the linked PEM hydrogen production module for controlling the flow rate of the preheated desalted water and/or the process steam required by the ATR hydrogen production module at the outlet of a desalted water or/and steam storage tank 2 With H-containing from PSA hydrogen-stripping module 2 H-containing desorbing gas or/and PEMFC module in PEMFC subsystem 2 H in exhaust gas 2 Concentration and flow are mainly controlled by combustion reaction and reaction temperature in a combustion chamber of an ATR reformer/reactor in an ATR hydrogen production module.
Furthermore, the cogeneration system for coupling the natural gas steam self-heating conversion with the water electrolysis mixed motion hydrogen production and the fuel cell is characterized in that the PEM hydrogen production module and the ATR hydrogen production module in the HHP subsystem preheat desalted water/process steam, raw material natural gas and O of the PEM hydrogen production module by switching and closing 2 H-containing of PEMFC module in desorption gas/PEMFC subsystem of PSA hydrogen extraction module 2 The connection between the waste gas pipeline and the logistics pipeline is independently operated, wherein, the H of the PSA hydrogen-extracting plate block 2 The air flow rate of the product is respectively takenThe purity of the produced hydrogen is 99.0 to 99.99 percent based on the respective production of the PEM hydrogen production module and the ATR hydrogen production module 2 And contain H 2 The concentration is 80-90% of the maximum capacity of the shift gas and thus determines the cogeneration capacity of the CHP system.
Furthermore, the cogeneration system for coupling the natural gas steam self-heating conversion with the water electrolysis mixed motion hydrogen production and the fuel cell is characterized in that in an ATR hydrogen production module in the HHP subsystem, O from a PEM hydrogen production module is regulated and controlled on the premise that the pre-conversion gas flow is unchanged 2 Flow and new addition of H from PEM hydrogen production module without gas-liquid separation and catalytic deoxygenation 2 The flow rate of the high-temperature converted gas entering the combustion chamber of the ATR reformer/reactor is changed to produce the synthesis gas and H 2 A hydrocarbon ratio of conversion gas required downstream, wherein, with O 2 H and H 2 Flow rate is increased to convert H in gas 2 The higher the concentration is, the stability is achieved after 90 percent is reached, or under the working condition of gas synthesis gas at the outlet of an ATR reformer in an ATR hydrogen production module, the synthesis gas does not need to undergo medium-high temperature conversion reaction, or directly enters a Palladium Membrane Separation (PMS) hydrogen extraction module for replacing a PSA hydrogen extraction module for H purification after heat exchange and temperature reduction 2 Purified H 2 Then enters the PEMFC subsystem for cogeneration, or the synthesis gas is used as raw gas after heat exchange to directly enter a Solid Oxide Fuel Cell (SOFC) subsystem for replacing the PEMFC subsystem for cogeneration, wherein H generated by a PEM hydrogen production module in the HHP subsystem 2 With O 2 Besides regulating the composition of the synthesis gas generated by the ATR hydrogen production module, the SOFC module which is also input into the SOFC subsystem is used for regulating the output power and the heat of the CHP cogeneration system consisting of the HHP subsystem and the SOFC subsystem, and the output power and the heat are 10-40% higher than those of the CHP system consisting of the original HHP subsystem and the PEMFC subsystem, but the output capacity is limited to be less than 1 MW.
Furthermore, the cogeneration system for coupling natural gas steam self-heating conversion with water electrolysis mixed motion hydrogen production and fuel cells is characterized in that the HHP subsystemThe original reforming conversion catalyst bed layer in the ATR reformer/reactor in the ATR hydrogen production module in the system is divided into two layers, the upper layer is kept with the original catalyst, the lower layer is filled with the double-function conversion and conversion catalyst, and O is kept to be introduced 2 The flow rate is unchanged, and the flow rate of natural gas fuel gas from an energy source raw material module of the HHP subsystem and/or desorption gas from the PSA hydrogen extraction module and/or hydrogen-containing tail gas from a PEMFC module of the PEMFC subsystem is increased, so that the CO content in converted gas flowing out of a reformer/reactor of the ATR hydrogen production module is less than 3-5%, the converted gas directly enters the PSA hydrogen extraction module after heat exchange without medium-high temperature conversion reaction, wherein the loading amount of a special CO molecular sieve is required to be increased in a composite adsorbent loaded in a PSA adsorption tower/device, and the H flowing out of the PSA hydrogen extraction module 2 And then enters the PEMFC subsystem for cogeneration.
Furthermore, the hybrid hydrogen production system with natural gas and water vapor self-heating conversion and proton exchange membrane water electrolysis coupling is characterized in that an ATR hydrogen production module in the HHP subsystem, or a two-section sleeve type Composite Conversion (CCSMR) hydrogen production module, or a two-section heat transfer type conversion (HTCR) hydrogen production module, or a heat exchange type conversion (HETR) hydrogen production module, or a combined conversion (USR) hydrogen production module, or a membrane reforming reaction (MSMR) hydrogen production module is used for replacement, a PEM hydrogen production module in the HHP subsystem, or a solid oxide water electrolysis (SOFC) hydrogen production module, or a basic water electrolysis (ALK) hydrogen production module is used for replacement, and the PEMFC subsystem, a Solid Oxide Fuel Cell (SOFC) hydrogen production subsystem is used for replacement, wherein a CCSMR, or/and HETR, or/and a HHP subsystem consisting of a HTCR hydrogen production module and a heat exchange type conversion (HETR) hydrogen production module is used for combination with the CHP hydrogen production system, a working medium is a heat and power cogeneration system of natural gas and an SOFC, and an ALK hydrogen production system is formed by the highest power and a high power and energy, and a MW power generation system is not used for the generation of the thermal power system, but the thermal power generation system is formed by the highest MW power and the thermal power generation system is combined with the SOFC system, and the thermal power generation system is high in the power generation system is used for the PEFC 1.
Furthermore, the natural gas steam self-heating conversion and water electrolysis mixed motion hydrogen production and fuel cell coupled heatThe power supply system is characterized in that a program control valve and a regulating valve group which are connected with each adsorption tower/device in a PSA hydrogen extraction module in the HHP subsystem are replaced by a multi-channel rotary valve, wherein an inlet and an outlet of each adsorption tower/device are connected with an inlet and an outlet of an upper disc and a lower disc of the multi-channel rotary valve, and the inlet and the outlet of the PSA hydrogen extraction module comprise H which is produced by the PEM hydrogen production module and has purity of 99.0-99.99 percent and is subjected to gas-liquid separation and catalytic deoxidation 2 With H-containing gas generated from an ATR hydrogen production module 2 80-90% concentration of shift gas and H flowing out of PSA hydrogen extraction module 2 The product gas and the desorption gas, the flushing gas and the vacuum pumping gas, and the process gas including the uniform pressure gas, the sequential deflation gas, the final inflation gas and the flushing gas in the system in the PSA hydrogen extraction module flow uniformly to enter and exit each adsorption tower/device through the corresponding channels and pipelines in the multi-channel rotary valve, wherein the number of times of pressure equalizing is at most 2 and at least 1 time, so that the PSA hydrogen extraction module is suitable for miniaturized skid-mounted, the hydrogen extraction yield is higher than 85-90%, and the improvement of the cogeneration capability of the CHP system is facilitated.
Furthermore, the natural gas steam self-heating conversion and water electrolysis mixed motion hydrogen production and fuel cell coupled cogeneration system is characterized in that the raw natural gas in an energy raw material module in the HHP subsystem is changed into renewable biomass methane as raw material gas, the methane from anaerobic fermentation is used as raw material gas, the raw material gas is input into a dry or wet crude desulfurization pre-purification process through a blower, the crude purified methane enters a PSA methane concentration system consisting of a plurality of adsorption towers which are connected in series/in parallel and are loaded with a fixed adsorbent bed layer mainly comprising carbon molecular sieves, the desorption gas generated by vacuumizing is directly discharged, the methane concentration gas generated by the desorption gas is more than or equal to 92%, and the methane content is introduced into an ATR hydrogen production module of the HHP subsystem as raw material gas to produce hydrogen, so that the cogeneration capacity of the whole CHP system is improved, and meanwhile, the cost is lower, the operation and standby power of the PEM or ALK or hydrogen production module are directly generated and supplied, and the operation fluctuation and elasticity of the PEM or SOFC module are particularly suitable for hydrogen production.
The beneficial effects of the invention are as follows:
(1) The invention adopts a novel Combined Heat and Power (CHP) system formed by organically coupling a mixed motion hydrogen production (HHP) subsystem formed by combining natural gas steam self-heating conversion hydrogen production and water electrolysis hydrogen production and a Proton Exchange Membrane Fuel Cell (PEMFC) subsystem, and has the advantages of large combined heat and power capability, high efficiency, strong stability, high coupling degree, small pollution, integrated skid-mounted integration, capability of switching the hydrogen production mode according to the raw material natural gas or electric power market and regional supply condition, no consumption of natural gas as fuel gas and the like compared with the existing CHP system for coupling the natural gas steam conversion hydrogen production and the proton membrane fuel cell.
(2) The HHP subsystem of the invention ensures that the steam and energy generated by the self-heating conversion (ATR) hydrogen production module can provide needed preheated desalted water and/or process steam and/or heat for the PEM hydrogen production module and/or the follow-up PEMFC subsystem on the premise of self-sufficiency, overcomes the defects of long electric heating power consumption and heating time of the original PEM hydrogen production module or unbalanced heat of the PEMFC subsystem, and simultaneously fully utilizes the byproduct pure oxygen (O) generated by the PEM hydrogen production 2 ) H-containing generated by hydrogen extraction with process gas or with PSA and PEMFC subsystem 2 The desorption gas and the tail gas are subjected to non-catalytic partial oxidation and complete oxidation combustion reaction in a combustion chamber at the top of a reformer/reactor in the ATR hydrogen production module, and the generated reaction heat provides enough energy for steam reforming reaction and subsequent medium-high temperature shift reaction carried out by a reforming catalyst bed layer at the lower part of the reformer/reactor, so that the consumption and the flue gas emission of raw material fuel gas caused by the traditional hydrogen production fuel gas by the reforming conversion of natural gas and Steam (SMR) are greatly reduced, and the surplus heat and the preheating desalted water/steam/heat are simultaneously provided for the operation temperature or the energy required by the PEM hydrogen production module/PEMFC subsystem, thereby reducing the energy consumption and the exhaust emission of the whole HHP subsystem and the PEMFC subsystem, and greatly increasing the H 2 The yield of the product gas and the cogeneration capacity of the CHP system make up the problems of high cost and low conversion rate of the hydrogen production by the PEM water electrolysis and H 2 The total utilization rate of the product gas is more than 90-92%.
(3) Through the efficient coupling of the HHP hydrogen production subsystem and the PEMFC subsystem, two hydrogen production modes in the HHP subsystem can be flexibly switched and regulated according to the price and electricity price market conditions of natural gas in a hydrogen market region, so that the operation cost of the CHP system is further reduced, for example, when the electricity price is relatively low at night, the flow of desalted water/steam entering a PEM hydrogen production module of the HHP subsystem is increased through a steam control valve, the flow of steam matched with the raw material natural gas is reduced, the water electrolysis hydrogen production proportion is improved, the low cost and high stability of electricity hydrogen used by the PEMFC subsystem are ensured, and the CHP cogeneration system can continuously, stably and economically output and output; the hydrogen production proportion of natural gas can be improved in turn in electricity deficiency seasons; the hydrogen production proportion of natural gas is reduced and the hydrogen production proportion of water electrolysis is increased in places with higher requirements on environment. In addition, the invention can independently operate water electrolysis hydrogen production or natural gas hydrogen production for a period of time so as to cope with fluctuation of natural gas and electric power markets and ensure stable and efficient operation of the CHP system.
(4) In the CHP system, the composition of the converted gas of the HHP subsystem can be flexibly adjusted, the synthesis gas is generated, hydrogen is extracted through the palladium membrane system, or/and a more advanced Solid Oxide Fuel Cell (SOFC) subsystem is directly adopted to replace the PEMFC subsystem to be suitable for H2 or synthesis gas for cogeneration, the efficiency is higher, the occupied area under the same scale is smaller, and the system is further suitable for distributed hydrogen production and cogeneration of a household or resident building with the power of less than 1 MW.
(5) The invention can utilize diversified energy sources, including clean energy sources such as water power, thermoelectric power, photoelectricity, wind power, nuclear power and the like, natural gas power generation, biomass biogas, solid waste thermoelectric power and the like which are recycled by low-carbon and waste resources, especially biomass biogas, not only can be used as raw material gas of an ATR hydrogen production module, but also can be used for generating power to provide partial power for water-power hydrogen production, and thermoelectric uses such as communities, hospitals and the like in the area where the combined heat and power of the CHP system is located are stably reversely supplemented, so that the direct electricity cost is reduced, and the friendly environment for the operation of the CHP system is further improved.
Drawings
Fig. 1 is a schematic flow chart of embodiment 1 of the present invention.
Fig. 2 is a schematic flow chart of embodiment 3 of the present invention.
Fig. 3 is a schematic flow chart of embodiment 4 of the present invention.
Detailed Description
In order to enable those skilled in the art to better understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
Example 1
As shown in figure 1, the natural gas steam autothermal reforming and water electrolysis hybrid hydrogen production and fuel cell coupled heat and power Cogeneration (CHP) system consists of an energy source raw material module, a proton exchange membrane water electrolysis (PEM) hydrogen production module, a natural gas steam autothermal reforming (ATR) hydrogen production module, a Pressure Swing Adsorption (PSA) hydrogen extraction module, a Hybrid Hydrogen Production (HHP) subsystem formed by pipelines, valves and heat exchangers among the modules, a proton membrane fuel cell (PEMFC) module, an alternating current-direct current conversion (DC/AC) module and a Waste Heat Recovery (WHR) module, and a proton membrane fuel cell (PEMFC) subsystem formed by pipelines, valves and heat exchangers among the modules, wherein the specific flow of the CHP heat and power cogeneration system formed by the HHP subsystem and the PEMFC subsystem is as follows,
(1) Energy source raw material module, from city natural gas with temperature of normal temperature and pressure of 0.3-0.6 MPa, flow rate of 1,000 standard square/hour (Nm) 3 And/h), all of which are used as raw material gas and are pressurized by a compressor to
2.0-2.2 MPa and preheating to 240-320 ℃, then entering into hydrodesulfurization, and partially obtaining H with purity of 99.8% from PEM hydrogen production module and after gas-liquid separation and catalytic deoxidation 2 As hydrogenation source, the purified raw material gas after hydrodesulfurization by using zinc oxide as catalyst is mixed with middle-low pressure steam which is taken as process steam from a steam storage tank and through a bypass throttle valve to form natural gas steam mixed steam, the natural gas steam mixed steam enters an ATR hydrogen production module, and O flows out from a PEM hydrogen production module 2 Desorption gas as combustion gas and purge gas from PSA hydrogen module and purge gas from PEMFC subsystem effluent
H 2 The tail gas is supplementary fuel gas, the combustion chamber at the top of the self-heating converter in the ATR hydrogen production module and the process conversion gas, or/and the desorption gas containing hydrogen and the tail gas are used as the combustion gas to carry out non-catalytic partial oxidation and complete oxidation combustion reaction, the generated reaction heat is heat provided by the converter, the preheating converter, desalted water vapor, the steam drum, the waste heat boiler and the medium-high temperature conversion reaction in the ATR module, the heat is derived from city tap water, and the desalted 5-10% desalted water is used as cooling water to enter
The converter of the ATR hydrogen production module carries out water jet cooling, flows out from a converter jacket and returns to urban tap water for recycling through heat exchange, 90-95% desalted water is preheated to 70-90 ℃ and then enters the deaerator of the ATR hydrogen production module as process water and is regulated by a hot water pump, wherein 20-40% of preheated desalted water is used as a working medium and is input into the PEM hydrogen production module, the rest 60-80% of fresh desalted water steam formed by a steam boiler and the ATR hydrogen production module form process steam which is used as process steam of an energy source raw material module, the process steam which flows out of the steam generator is regulated by a bypass valve and is mixed with purified and desulfurized natural gas to form mixed steam which is then enters the ATR hydrogen production module, meanwhile, a throttle jet regulating valve connected with the PEM hydrogen production module is closed, high-temperature flue gas which is regularly discharged from a converter combustion chamber of the ATR hydrogen production module and the PEM hydrogen production module is subjected to cold-hot heat exchange and gas-liquid separation, water returns to the pretreatment and is recycled, and gas is discharged as waste gas, and the power from an urban power grid is directly connected into a control system of the PEM hydrogen production module to provide needed for starting and hydrogen production;
(2) The PEM hydrogen production module is characterized in that when the power input from the energy source raw material module is connected with a control system consisting of a transformer and a control cabinet, under the working condition that working medium is liquid water, preheated desalted water with the temperature of 70-90 ℃ flowing out of a water storage tank is input into an electrolytic tank of the PEM hydrogen production module through a regulating valve, the operation temperature of the electrolytic tank is 70-90 ℃, the precipitation concentration of the anode of an exchange membrane of the electrolytic tank is 99%, and the pressure is
2.0 to 2.2MPa of O 2 Cooling the mixture by a cooler, then entering an oxygen storage tank, outputting the cooled mixture as fuel gas, entering an ATR hydrogen production module, and separating out the mixture with the concentration of 99.2-99.9% and the pressure of the mixture from the cathode of an electrolytic tank
H of 2.0-2.2 MPa 2 After water is removed by a water-gas separator, 3 to 5 percent of H is used as the hydrogen desulfurization of the raw material natural gas of the energy raw material module 2 The source and the rest directly enter a PSA hydrogen extraction module for H 2 Purifying and preparing product gas;
(3) The ATR hydrogen production module comprises a mixed steam formed by mixing purified natural gas raw gas from an energy raw material module with steam flowing out of a steam storage tank and water steam through a bypass throttle valve, a pre-conversion gas formed by preheating through a convection type preheater, a combustion chamber arranged at the upper part of the ATR converter, and 99.0% O from a PEM hydrogen production module 2 And H-containing from a PSA hydrogen-stripping module as a make-up fuel gas 2 Desorption gas
H-containing flow out of PEMFC subsystem 2 The tail gas is subjected to non-catalytic partial oxidation and complete oxidation combustion reaction, the generated combustion heat is directly fed into a reforming conversion reaction by high-temperature gas which is formed by reactants and has the temperature of 850-950 ℃ and is loaded with a nickel/nickel series reforming conversion catalyst bed layer positioned at the lower part of a combustion chamber, the conversion reaction temperature is 850-950 ℃, and the conversion reaction pressure is
2.0-2.2 MPa, the converted gas is cooled, heat-exchanged by a steam drum and a waste heat boiler to supply heat for desalination process steam, and then enters a medium-temperature shift reaction, the shift reaction temperature is 260-350 ℃, and the reaction pressure is
2.0-2.2 MPa, the converted gas is converted into converted gas after medium-high temperature conversion reaction, the composition of the converted gas is as follows,
85～90％H 2 carbon dioxide (CO) 9-15% 2 ) Carbon monoxide (CO) less than 1% and residual trace hydrocarbon impurities, and the converted gas enters a PSA hydrogen extraction module for hydrogen extraction after heat exchange with boiler feed water and desalted water;
(4) PSA hydrogen extraction module, purity from PEM hydrogen production module is 99.2-99.9%, pressure is
H of 2.0-2.2 MPa 2 Removing water by a water-gas separator, and then carrying out catalytic deoxidation, heat exchange and coolingH after cooling 2 With H from ATR hydrogen-producing module 2 The converted gas with the concentration of 85-90% is respectively or mixed into a pressure swing adsorption formed by 5 composite adsorbent beds which are connected in series and loaded with aluminum oxide, silica gel, active carbon and molecular sieve and formed by pipelines between adsorption towers, program control valves and regulating valve groups
(PSA) system with adsorption pressure of 2.0-2.2 MPa and adsorption temperature of 20-60 deg.C, and 5 adsorption towers alternately switched to adsorption, sequential discharge, 2 times of pressure equalizing and lowering, reverse discharge, vacuumizing and flushing, and 2 times of pressure equalizing and lowering
The adsorption and desorption circulation operation of the secondary uniform pressure rising and final filling steps adopts a slow uniform mode, wherein,
the flushing gas adopts product gas, and the final aeration adopts H from PEM hydrogen production module after gas-liquid separation and catalytic deoxidation 2 From this, H with a purity of 99.9995% was obtained 2 Product gas, pressure of
2.0-2.2 MPa, temperature of 20-60 ℃ and flow rate of 1800-2000 Nm 3 /H, enter H 2 The product gas tank is used as raw gas to directly enter a subsequent PEMFC subsystem for cogeneration, and the desorption gas obtained from the raw gas enters a buffer tank and is used as supplementary fuel gas to be returned to the ATR hydrogen production module for recycling, thereby H 2 The total yield of the product gas is more than or equal to 93 percent.
(5) PEMFC module, H2 with purity of 99.9995% from PSA hydrogen extraction module in HHP subsystem
Product gas enters a proton membrane fuel cell (PEMFC) module in a PEMFC subsystem, wherein the PEMFC fuel cell consists of more than 10 cell groups connected in parallel with a current collecting plate, a single cell consists of a membrane electrode (anode, cathode and proton exchange membrane) and the current collecting plate, and the pressure of H from a PSA hydrogen extraction module is 2.0-2.2 MPa 2 And O from PEM hydrogen production module with pressure of 2.0-2.2 MPa 2
Respectively enter the anode and the cathode of the battery, reach the interface of the Catalytic Layer (CL) and the Proton Exchange Membrane (PEM) through the diffusion layer, respectively undergo oxidation and reduction reactions under the action of Pt catalyst, and the reaction temperature is 70-90 ℃. At anode, H 2 Electrochemical reaction takes place to generate hydrogen ions (protons) and electronsWherein electrons are conducted to the cathode through a loaded external circuit and protons migrate through an electrolyte in the proton exchange membrane to the cathode, thereby outputting Direct Current (DC) at the external circuit and into
An alternating current-to-direct current (electric) conversion (DC/AC) module of the PEMFC subsystem, and hydrogen ions, electrons and oxygen react at a cathode to generate water. 50 to 70 percent of the redundant hydrogen-containing waste gas flowing out from the anode of the battery is used as the supplementary fuel gas and returned to the ATR hydrogen production module of the HHP subsystem for recycling, and 30 to 50 percent
After gas-liquid separation and catalytic deoxidation of the PEM hydrogen production module, H generated by the PEM hydrogen production module 2 Mixing and feeding the mixture into a PSA hydrogen extraction module for further recovering H 2 The generated water is discharged from the cathode outlet along with the redundant oxygen in the form of water vapor and hot water and enters the waste heat recovery of the PEMFC subsystem
(WHR) module.
(6) And the DC/AC module is used for converting the direct current from the PEMFC module into alternating current through the configured alternating current-direct current converter, outputting about 1.2-1.5 MW of output power, or directly surfing the Internet, or inputting the output power into each user for use.
(7) The WHR module is used for regulating and mixing the steam or hot water from the PEMFC module and about 5-10% of steam and preheated water from the HHP subsystem through a steam tank or a preheated water regulating valve connected with the HHP subsystem, then entering a heat management unit consisting of a heat exchanger and a circulating cooling water circulating pump, outputting hot water with the temperature of about 35-60 ℃ formed by exchanging heat with the mixed steam and the preheated water through a heat exchanger from a tap water pipe network of a user to the user for direct use, and outputting the heat load of about 1.5-1.8 MW, wherein the CHP cogeneration load management mode is mainly used for supplying the user with heat load management, so that the heat balance of the HHP subsystem is easy to achieve, the hydrogen production capacity of the HHP subsystem is ensured to be stable, the operation of the CHP cogeneration system is finally enabled to reach a stable state, the consumption of natural gas is minimum, and the cogeneration efficiency is optimal.
Example 2
As shown in fig. 1, in the embodiment 1, the energy source material modules in the HHP subsystem are from the group consisting of normal temperature and pressure0.3MPa of industrial natural gas, the flow of which is 1,000Nm 3 The/h is adjusted to 500Nm 3 And/h, all raw material gas and O produced by PEM hydrogen production module 2 And stripping gas produced by the PSA hydrogen extraction module and H-containing gas produced by the PEMFC subsystem 2 The tail gas is used as fuel gas, the corresponding desalted water vapor amount is only adjusted to 60-70% of the original one, wherein the ratio of desalted water and corresponding vapor entering the PEM hydrogen production module to ATR hydrogen production module is 3:7, the water-carbon ratio of the reformer reaction in the ATR hydrogen production module is increased, the conversion reaction temperature is 880-980 ℃, the operating temperature of the electrolyzer in the hydrogen production module is 70-90 ℃, the hydrogen evolution amount is unchanged, the gas-liquid separation and catalytic deoxidation are carried out, the gas-liquid separation and the converted gas from the ATR hydrogen production module are mixed, the mixed gas enters the PSA hydrogen extraction module for hydrogen extraction, an adsorption tower of the PSA hydrogen extraction module is changed into a 4 tower from a 5 tower, the cyclic operation process of adsorption-sequential release-secondary uniform pressure drop-reverse release-vacuumizing-vacuum flushing and backfilling (pressure) -secondary pressure equalizing rising-final charging, the flushing gas is sequential gassing, and the final charging gas is H from the PEM hydrogen production module 2 Thus, H with a purity of 99.999% was produced from the PSA hydrogen extraction module 2 The flow rate of the product gas is 1000-1200 Nm 3 and/H, wherein H is produced by the PEM hydrogen production module 2 The product gas accounts for 25-30%, which is improved by 30-40% compared with the embodiment 1, meanwhile, the steam/preheated water flowing out of the PEMFC module in the embodiment 1 independently enters the WHR module, and the original about 5-10% steam/preheated water from the HHP subsystem is not mixed with the steam/preheated water flowing out of the PEMFC module and is totally used for the HHP subsystem, so that the power supply and heat supply capacity of the whole CHP cogeneration system are respectively 0.7-0.9 MW and 0.9-1.1 MW, and meanwhile, the proportion adjustment of the hydrogen production by self-heating conversion of the proton exchange membrane water electrolysis hydrogen production and the natural gas steam in the hybrid hydrogen production system is realized.
Example 3
As shown in fig. 2, on the basis of example 1, the pre-conversion gas flow in the ATR hydrogen production module was unchanged by increasing O from the PEM hydrogen production module in the HHP subsystem 2 10% of the original flow and a new increase in the flow to about 5% of the flow from the PEM hydrogen production module without gas-liquid separation and catalytic deoxygenationH 2 The flow rate into the combustion chamber of the ATR reformer/reactor is varied to alter the composition of the exiting high temperature reformed gas such that H in the reformed gas 2 Concentration increases, ultimately leading to H in the shift gas 2 The concentration is 86-90%, the concentration of CO is 5-8%, and a quasi-synthetic gas composition is formed. Meanwhile, the 'quasi-synthesis gas' does not need to be subjected to medium-high temperature conversion and PSA hydrogen extraction module, but is replaced by adopting a palladium membrane unit connected in series with two stages, namely, the quasi-synthesis gas is subjected to heat exchange and temperature reduction to 60-90 ℃ and pressure of 2.0-2.2 MPa, enters a first-stage palladium membrane, and is subjected to permeation side flow to obtain H with purity of 97-98% 2 Pressurizing and then entering a second-stage palladium membrane, and flowing out H with the purity of 99.99% from the permeate side 2 Product gas is then fed into the SOFC subsystem composed of the PEMFC module of the Solid Oxide Fuel Cell (SOFC) alternative embodiment 1, electricity and heat are output therefrom for use by users, the non-permeate gas flowing out of the non-permeate side of the primary palladium membrane is directly returned to the ATR hydrogen production module of the HHP subsystem as fuel gas, the non-permeate gas flowing out of the non-permeate side of the secondary palladium membrane is directly discharged, the same amount of SOFC fuel cell is correspondingly increased by about 6-9%, and about 10% of water vapor formed therefrom is used for returning to the HHP subsystem, and the rest of the steam is used for heat recovery of the WHR module of the SOFC subsystem, thereby reducing the volume of the whole CHP cogeneration system by about 1/5-1/4 on the basis of increasing about 10% of cogeneration capacity.
Example 4
As shown in fig. 3, based on example 1, the raw gas of the energy source raw material module in the HHP subsystem is changed from natural gas into biogas, and the biomass anaerobic fermentation biogas flowing out of the gas holder or the air bag has a typical component of methane (CH) 4 ) 65% (v/v), carbon dioxide (CO) 2 ) 30-34%, the rest impurities are 1-3%, and the flow is 1000Nm 3 And (h), wherein the sulfur content is about 800ppm, the sulfur is pressurized to 30kPa by a Roots blower and then enters the lower part of the wet desulfurization tower, the sulfur is contacted with desulfurization lean solution from top to bottom on the surface of the filler, various reductive and acidic gas desulfurization solutions are absorbed, the solution is oxidized by spraying and sucking air, the regeneration is obtained, sulfur foam is separated, and the clear desulfurization solution after foam separation is carried outCan be recycled, sulfur foam further enters a sulfur melting kettle to prepare sulfur, and hydrogen sulfide (H) in the methane after coarse desulfurization 2 S) the content of S) is less than 300ppm, the methane after coarse desulfurization is further desulfurized by using two dry ferric oxide adsorption desulfurization towers, wherein 1 adsorption desulfurization tower is in an adsorption state, and the other 1 tower is in a standby state, the coarse desulfurized methane enters from the lower part of the desulfurization adsorption tower and passes through a ferric oxide filler layer in the desulfurization tower to carry out H treatment on the methane 2 S is absorbed or absorbed and reacted into sulfide or polysulfide to be remained in the packing layer, methane is discharged from the top of the desulfurization tower after pre-purification, and H in the methane is discharged from the top of the desulfurization tower 2 The S content is less than or equal to 25ppmv, the pre-purified biogas is pressurized to 0.6MPa by a compressor, then enters a gas-water separator to remove free water and oil, then enters a PSA methane concentration system consisting of 6 adsorption towers, and the adsorption towers are filled with a composite adsorbent comprising activated carbon mainly comprising carbon molecular sieve and aluminum oxide by vacuum desorption, and CO in methane concentration gas flowing out of the adsorption towers 2 Less than or equal to 3 percent (v/v), and the whole raw gas is used as the raw gas of the subsequent ATR hydrogen production module, is pressurized to 2.0-2.2 MPa by a compressor and preheated to 240-320 ℃, and then enters into the hydrodesulphurization, and part of the H is obtained from the PEM hydrogen production module, the purity of which is 99.9 percent and is subjected to gas-liquid separation and/or catalytic deoxidation 2 As a hydrogenation source, the purified methane raw material gas obtained after the zinc oxide is used as a catalyst for hydrodesulphurization is mixed with medium-low pressure steam from an ATR hydrogen production module to form mixed steam of purified methane concentrated gas and steam, the mixed steam enters the ATR hydrogen production module for hydrogen production, the power of the energy raw material module is generated by methane, sufficient power is provided for a PEM hydrogen production module, the PEM hydrogen production module is suitable for operation of a methane generator set with power generation capability fluctuation, the hydrogen generation capability of the PEM hydrogen production module is kept stable, and finally H with the purity of 99.995% is produced from an HHP subsystem 2 The gas flow of the product is 1,200 to 1,400Nm 3 And (h) entering the PEMFC subsystem to perform cogeneration.
It will be apparent that the embodiments described above are only some, but not all, of the embodiments of the present invention. All other embodiments, or structural changes made by those skilled in the art without inventive effort, based on the embodiments described herein, are intended to be within the scope of the invention, as long as the same or similar technical solutions as the invention are provided.
Claims (8)
1. A natural gas steam self-heating conversion and water electrolysis mixed motion hydrogen production and fuel cell coupled cogeneration system is characterized in that the Cogeneration (CHP) system consists of a mixed motion hydrogen production (HHP) subsystem and a proton membrane hydrogen fuel cell (PEMFC) subsystem, wherein the HHP subsystem consists of an energy source raw material module, a proton exchange membrane water electrolysis (PEM) hydrogen production module, a natural gas steam self-heating (ATR) hydrogen production module, a Pressure Swing Adsorption (PSA) hydrogen extraction module and pipelines, valves and heat exchangers among the modules, the PEMFC subsystem mainly consists of the PEMFC module, a power conversion (DC/AC) module, a Waste Heat Recovery (WHR) module and pipelines, valves and heat exchangers among the modules, wherein the main flow of the CHP system is that natural gas and desalted water from a city or industrial pipe network enter the HHP subsystem as raw materials, the energy source raw material module and the ATR module of the raw material natural gas and the desalted water enter the HHP subsystem in sequence, the hydrogen concentration is 80-90% (PEM/v) and the purity of 80-99.99% (99.99/99.99% of hydrogen is produced from the intermediate flow rate conversion module and the purity of the hydrogen is 99.99.99/99% of the intermediate purity of the hydrogen produced by the conversion module 2 The product gas enters a PEMFC module of a PEMFC subsystem, direct current output from the PEMFC module outputs alternating current with power of 10 kW-10 MW through a DC/AC module, or is directly used by regional users or is combined with a power grid for use, waste heat generated by the PEMFC module is recycled through a WHR module to output heat of 12 kW-15 MW, a part of the heat is used by regional users for hot water use, a part of the heat is returned to a HHP subsystem for use, the generated cooling water is mixed with the cooling water of the HHP subsystem for recycling after treatment, and the generated H-containing heat is recycled 2 The tail gas is returned to the HHP subsystem as fuel gas, and O with the concentration of 98.5-99.5% (v/v) is generated from a PEM hydrogen production module in the HHP subsystem 2 As fuel gas, a part of the fuel gas is input into an ATR hydrogen production module in the HHP subsystem and a part of the fuel gas is input into a PEMFC module in the PEMFC subsystem, and the fuel gas is generated from a PSA hydrogen extraction module in the HHP subsystemPart of the hydrogenolysis gas is used as fuel gas to be returned to the ATR hydrogen production module in the HHP subsystem, and the other part is directly discharged after being treated as exhaust gas.
Wherein, in the HHP subsystem, the energy source raw material module is used for preprocessing natural gas raw materials, treating electric energy, process water, boiler water and steam, optimizing each raw material component and energy to adapt to the requirements of a downstream module, and comprises an ATR hydrogen production module used as raw material natural gas and an PSA hydrogen extraction module used for generating H-containing gas 2 The desorption gas is the supplementary fuel gas, pure oxygen gas, hydrodesulfurization gas, desalted water and steam storage tank, normal temperature or heater or heat exchanger, normal pressure or booster, raw material natural gas desulfurization and treatment of mixed steam of raw material gas and process water, natural gas generator or water and electricity or other power supply, process water and boiler water desalination pretreatment, circulating pump and heat exchange, and process raw materials inside and outside the module, pure oxygen fuel, inlet and outlet pipelines of an electric power pipe network and control valves; the PEM hydrogen production module consists of a one-stage or multistage serial/parallel proton exchange membrane water electrolyzer, a water storage tank/steam tank, a gas-liquid processor, a rectifier, an electric heater, a control system, a throttle valve, a bypass valve and hydrogen (H) 2 ) With oxygen (O) 2 ) Gas cooler, H 2 Catalytic deoxidizer, and power and H connected inside and outside module 2 、O 2 The ATR hydrogen production module comprises a preheating converter of mixed steam, an ATR reformer/reactor with a combustion chamber at the top, a medium-high temperature shift reactor, a gas-liquid separator, a heat exchanger, a steam drum, a waste heat boiler, mixed steam, converted gas, shift gas, fuel gas, PSA stripping hydrogen absorption gas pipeline, desalted water, boiler water supply, a steam storage tank, a cooling circulating water pipeline, a conveying and circulating pump and a control valve, wherein the mixed steam, the converted gas, the shift gas, the fuel gas, the PSA stripping hydrogen absorption gas pipeline, the desalted water are connected inside and outside the module; the PSA hydrogen extracting module consists of a plurality of adsorption towers connected in series/parallel, a desorption gas buffer tank, and electric power and H connected inside and outside the module 2 Product gas/stripping gas, H flowing out of PEM hydrogen production module 2 The device comprises a conversion gas pipeline, a program control valve and a regulating valve group, wherein the conversion gas pipeline flows out of the ATR hydrogen production module.
2. A cogeneration system for coupling natural gas steam autothermal reforming with water electrolysis hybrid hydrogen production and fuel cells in accordance with claim 1 wherein the purity of the hydrogen production module of the PEM in the HHP subsystem is 99.0-99.99% and is either directly or catalytically deoxygenated H 2 H-containing produced with ATR hydrogen production module 2 The ratio of the converted gas with the concentration of 80-90% is 1-4:6-9, and the proportion is prepared by desalted water/process steam, raw material natural gas/fuel gas, process conversion gas and O of a PEM hydrogen production module 2 And/or PSA hydrogen extraction module and/or H-containing of PEMFC module in PEMFC subsystem 2 The control of the usage amount of desorption gas as the supplementary fuel gas flowing out of the waste gas is obtained, wherein the distribution of the flow rates of the process steam entering the ATR hydrogen production module and the preheated desalted water entering the PEM hydrogen production module and the O from the PEM hydrogen production module are controlled by controlling the opening of a water supply pump outlet or/and a bypass steam throttle valve or the opening of a high-temperature steam throttle valve of the linked PEM hydrogen production module for controlling the flow rate of the preheated desalted water and/or the process steam required by the ATR hydrogen production module at the outlet of a desalted water or/and steam storage tank 2 With H-containing from PSA hydrogen-stripping module 2 H-containing desorbing gas or/and PEMFC module in PEMFC subsystem 2 H in exhaust gas 2 Concentration and flow are mainly controlled by combustion reaction and reaction temperature in a combustion chamber of an ATR reformer/reactor in an ATR hydrogen production module.
3. The cogeneration system of the natural gas steam autothermal reforming and water electrolysis hybrid hydrogen production and fuel cell coupling of claim 1 wherein the PEM hydrogen production module and ATR hydrogen production module in the HHP subsystem are configured to preheat the desalted water/process steam, feed natural gas and O of the PEM hydrogen production module by switching and switching off the PEM hydrogen production module and ATR hydrogen production module 2 H-containing of PEMFC module in desorption gas/PEMFC subsystem of PSA hydrogen extraction module 2 The connection between the waste gas pipeline and the logistics pipeline is independently operated, wherein, the H of the PSA hydrogen-extracting plate block 2 The product gas flow rate was 99 depending on the respective output purities of the PEM hydrogen production module and the ATR hydrogen production module.0～99.99％H 2 And contain H 2 The concentration is 80-90% of the maximum capacity of the shift gas and thus determines the cogeneration capacity of the CHP system.
4. The cogeneration system of claim 1 wherein the pre-conversion gas flow is controlled by controlling the O from the PEM hydrogen production module without changing the ATR hydrogen production module in the HHP subsystem 2 Flow and new addition of H from PEM hydrogen production module without gas-liquid separation and catalytic deoxygenation 2 The flow rate of the high-temperature converted gas entering the combustion chamber of the ATR reformer/reactor is changed to produce the synthesis gas and H 2 A hydrocarbon ratio of conversion gas required downstream, wherein, with O 2 H and H 2 Flow rate is increased to convert H in gas 2 The higher the concentration is, the stability is achieved after 90 percent is reached, or under the working condition of gas synthesis gas at the outlet of an ATR reformer in an ATR hydrogen production module, the synthesis gas does not need to undergo medium-high temperature conversion reaction, or directly enters a Palladium Membrane Separation (PMS) hydrogen extraction module for replacing a PSA hydrogen extraction module for H purification after heat exchange and temperature reduction 2 Purified H 2 Then enters the PEMFC subsystem for cogeneration, or the synthesis gas is used as raw gas after heat exchange to directly enter a Solid Oxide Fuel Cell (SOFC) subsystem for replacing the PEMFC subsystem for cogeneration, wherein H generated by a PEM hydrogen production module in the HHP subsystem 2 With O 2 Besides regulating the composition of the synthesis gas generated by the ATR hydrogen production module, the SOFC module which is also input into the SOFC subsystem is used for regulating the output power and the heat of the CHP cogeneration system consisting of the HHP subsystem and the SOFC subsystem, and the output power and the heat are 10-40% higher than those of the CHP system consisting of the original HHP subsystem and the PEMFC subsystem, but the output capacity is limited to be less than 1 MW.
5. A cogeneration system for coupling natural gas steam autothermal reforming with water electrolysis hybrid hydrogen production and fuel cells in accordance with claim 1The method is characterized in that the bed layer of the original reforming conversion catalyst in the ATR reformer/reactor in the ATR hydrogen production module in the HHP subsystem is divided into two layers, the upper layer is kept with the original catalyst, the lower layer is filled with the double-function conversion and conversion catalyst, and O is kept to be introduced 2 The flow rate is unchanged, and the flow rate of natural gas fuel gas from an energy source raw material module of the HHP subsystem and/or desorption gas from the PSA hydrogen extraction module and/or hydrogen-containing tail gas from a PEMFC module of the PEMFC subsystem is increased, so that the CO content in converted gas flowing out of a reformer/reactor of the ATR hydrogen production module is less than 3-5%, the converted gas directly enters the PSA hydrogen extraction module after heat exchange without medium-high temperature conversion reaction, wherein the loading amount of a special CO molecular sieve is required to be increased in a composite adsorbent loaded in a PSA adsorption tower/device, and the H flowing out of the PSA hydrogen extraction module 2 And then enters the PEMFC subsystem for cogeneration.
6. The cogeneration system of claim 1 characterized in that the ATR hydrogen production module, or the two-stage sleeve-type composite reforming (CCSMR) hydrogen production module, or the two-stage heat transfer reforming (HTCR) hydrogen production module, or the heat exchange reforming (HETR) hydrogen production module, or the combined reforming (USR) hydrogen production module, or the membrane reforming reaction (MSMR) hydrogen production module is used for replacement, and the PEM hydrogen production module, or the solid oxide water electrolysis (SOFC) hydrogen production module, or the alkaline water electrolysis (ALK) hydrogen production module is used for replacement, in the HHP subsystem, and the PEMFC subsystem is replaced by the Solid Oxide Fuel Cell (SOFC) hydrogen production subsystem, wherein the HHP subsystem consisting of the CCSMR, the heat exchange reforming (HETR) hydrogen production module, or the SOFC hydrogen production module, and the high power energy, and the high power, combined heat energy, and the high energy, combined power, and high power, are generated by the combined heat and power, and the high energy, and the combined power, and the high power, but the combined power, hydrogen and the high power, heat and the high energy, and the combined power, and the high energy are generated by the proton and the combined power, and the proton and the fuel cell.
7. The cogeneration system of the natural gas steam autothermal reforming and hydro-electric hybrid hydrogen production and fuel cell coupling of claim 1 characterized in that the program control valve and the regulating valve group connected to each adsorption tower/device in the PSA hydrogen-extracting module in the HHP subsystem are replaced by a multi-channel rotary valve, wherein each adsorption tower/device inlet and outlet are connected with the inlet and outlet of the upper and lower discs of the multi-channel rotary valve, and the inlet and outlet PSA hydrogen-extracting module comprises H with purity of 99.0-99.99% generated by the PEM hydrogen-producing module and after gas-liquid separation and catalytic deoxidation 2 With H-containing gas generated from an ATR hydrogen production module 2 80-90% concentration of shift gas and H flowing out of PSA hydrogen extraction module 2 The product gas and the desorption gas, the flushing gas and the vacuum pumping gas, and the process gas including the uniform pressure gas, the sequential deflation gas, the final inflation gas and the flushing gas in the system in the PSA hydrogen extraction module flow uniformly to enter and exit each adsorption tower/device through the corresponding channels and pipelines in the multi-channel rotary valve, wherein the number of times of pressure equalizing is at most 2 and at least 1 time, so that the PSA hydrogen extraction module is suitable for miniaturized skid-mounted, the hydrogen extraction yield is higher than 85-90%, and the improvement of the cogeneration capability of the CHP system is facilitated.
8. The cogeneration system for coupling natural gas steam self-heating conversion with water electrolysis mixed motion hydrogen production and fuel cells according to claim 1, wherein the raw natural gas in an energy raw material module in the HHP subsystem is changed into renewable biomass biogas as raw material gas, the biogas from anaerobic fermentation is used as raw material gas, the raw material gas is input into a dry or wet crude desulfurization pre-purification process through a blower, the crude purified biogas is pressurized by a compressor and then enters a PSA methane concentration system consisting of a plurality of adsorption towers which are connected in series/in parallel and are loaded with fixed adsorbent beds mainly comprising carbon molecular sieves, the desorption gas generated by vacuum pumping and desorption is directly discharged, the methane concentration gas generated by the desorption gas is generated, the methane content is more than or equal to 92%, the methane concentration gas is generated by entering an ATR hydrogen production module of the HHP subsystem according to the natural gas as raw material gas, so that the cogeneration capacity of the whole CHP system is improved, and meanwhile, the operation and standby power of a PEM or ALK or hydrogen production module are supplied by direct power generation, and the operation and the standby power of the PEM or the SOFC module are particularly suitable for operation fluctuation and elasticity of the PEM.
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